EP3113879A1 - Catalyseurs de ruthénium-phénol pour réactions d'hydrogénation par transfert - Google Patents

Catalyseurs de ruthénium-phénol pour réactions d'hydrogénation par transfert

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Publication number
EP3113879A1
EP3113879A1 EP15707938.5A EP15707938A EP3113879A1 EP 3113879 A1 EP3113879 A1 EP 3113879A1 EP 15707938 A EP15707938 A EP 15707938A EP 3113879 A1 EP3113879 A1 EP 3113879A1
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Prior art keywords
alkyl
ruthenium
substituents
hydrogen
optionally substituted
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German (de)
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EP3113879B1 (fr
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Carolin Limburg
Rocco Paciello
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0202—Alcohols or phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/44—Allylic alkylation, amination, alkoxylation or analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention is directed towards a catalyst which is obtainable by contacting in situ a ruthenium precursor and a phenol derivative. Furthermore, the present invention is directed towards the use of said catalyst in transfer hydrogenation reactions. In particular, the present invention is directed to a method for preparing menthone starting from isopulegol.
  • Ruthenium transfer hydrogenation catalysts are known in the literature. These ruthenium catalysts all require specific ligands (e.g. phosphine, NHC-ligands, bipyridine ligands). The recycling behaviour of these ruthenium catalysts is not optimal. Their activity (Turnover frequency: TOF) diminishes with the increase of recycling-cycles and a high turnover number (TON) and thus a long life-cycle cannot be achieved.
  • TOF Trigger frequency
  • ruthenium catalysts with improved characteristics are still needed.
  • ruthenium catalysts which are readily accessible and with a long lifetime are highly desirable.
  • Ruthenium phenolate complexes have been reported in the literature. The synthesis of ruthenium phenolate complexes is described by Kondo et al. in Organometallics 2005, 24, 905-910. A ruthenium phenolate complex was prepared by reacting Ru( 7 6 -COT)(dmfm) 2 with phenol. The resulting complex was isolated.
  • Panichakul et al., Organometallics 2008, 27, 6390-6392 describes the synthesis of BINOLate complexes of ruthenium. Said BINOLate complexes were prepared by reacting [RuCl 2 -p-cymene] 2 with BINOL and isolated.
  • Ru(lll) complex compounds of alizarin The use of these complexes as UV absorbers was investigated. Catalytic properties have not been described.
  • a ruthenium catalyst which is obtainable by contacting in situ in a liquid medium a ruthenium precursor which has labile ligands and as further ligand a phenol derivative of formula (I)
  • R 1 , R 2 , R 3 independently are hydrogen, alkyl, or hydroxy
  • Y is a chemical bond, optionally substituted alkylene, optionally substituted arylene, -0-, or -S-;
  • R 4 is hydrogen, alkyl, hydroxy or optionally substituted aryl
  • R 3 , Y-R 4 together with the carbon atoms to which they are bound form an anellated aromatic ring
  • X is a chemical bond, optionally substituted alkylene, optionally substituted arylene, -0-, or -S-;
  • R 5 is hydrogen, alkyl, hydroxy, or an optionally substituted aryl, or R 5 , R 4 together are optionally substituted arylene.
  • said ruthenium precursor does not possess strong donor ligands such as nitrogen or phosphorous donor ligands.
  • the ruthenium catalyst according to the invention is useful to catalyse transfer hydrogenation reactions, in particular dehydrogenation/hydrogenation reactions.
  • the present invention further provides a method for preparing menthone wherein a dehydrogenation/hydrogenation reaction is carried out in the liquid phase using isopulegol, a ruthenium precursor which has labile ligands and a phenol derivative of formula (I) as defined above.
  • Liquid medium refers to an organic substance or a mixture of organic substances which are in the liquid state under the following conditions: T in the range from 100 to 220°C, preferably 150 to 200°C, more preferably 170 to 190°C; p in the range of 1 to 100 bar, preferably 1 to 50 bar, more preferably 1 to 10 bar.
  • Normal pressure is preferred, but overpressure can be adjusted to keep reaction components in the liquid phase.
  • Ruthenium precursor refers to a ruthenium compound which allows the coordination of phenols, i.p. of such of formula (I) above.
  • ruthenium precursor refers to ruthenium compounds which possess “labile” ligands.
  • the ruthenium precursors do not possess strong donor ligands such as nitrogen and phosphorous donor-ligands (in particular trivalent N and trivalent P ligands and N-heterocyclic carbene ligands).
  • Labile refers to the relative ability of the ligands to remain coordinated to the transition metal complex.
  • Non-limiting examples of labile ligands are halides, alkyl, olefins (e.g.
  • Halogen denotes fluorine, chlorine, bromine, iodine.
  • Halide denotes fluoride, chloride, bromide, iodide.
  • Alkyl represents a linear or branched alkyl group having 1 to 20, preferably 1 to 10 carbon atoms. Examples thereof are: CrC 4 -alkyl radicals selected from methyl, ethyl, prop-1 -yl, prop-2-yl, but-1 -yl, but-2-yl, 2-methylprop-1 -yl, or 2-methylprop-2-yl, or d- Cio-alkyl radicals selected from Ci-C 4 -alkyl radicals as defined above and additionally pent-1 -yl, 1 -methylbut-1 -yl, 2-methylbut-1 -yl, 3-methylbut-1 -yl, 2,2-dimethylprop-1 -yl, 1 -ethylprop-1 -yl, hex-1 -yl, 1 ,1 -dimethylprop-1 -yl, 1 ,2-dimethylprop-1 -
  • Substituted alkyl is an alkyl group as defined herein substituted with 1 , 2, 3, 4 or 5 substituents, in particular 1 , 2 or 3 substituents, preferably one substituent, which are independently selected from the group consisting of halogen, alkyl, substituted alkyl, cycloalkyl, aryl, and OH.
  • HandAlkylene represents a linear or branched divalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 4 as for example Ci-C 4 -alkylene groups, like -CH 2 -, - (CH 2 ) 2 -, -CH(CH 3 )-, and -C(CH 3 ) 2 -.
  • Substituted alkylene is an alkylene group as defined herein substituted with 1 , 2 or 3 substituents, preferably one substituent, which are independently selected from the group consisting of halogen, alkyl, substituted alkyl, cycloalkyl, aryl, and OH.
  • Cycloalkyl represents a 3- to 12- membered, in particular 3- to 6- membered cycloaliphatic radical. Examples thereof are C 3 -Ci 2 -cycloalky such as cyclopropyl, cyclobutyl, cyclo-pentyl and cyclohexyl.
  • the cyclic structure may be unsubstituted or may carry 1 , 2, 3 or 4 d-C 4 alkyl radicals, preferably one or more methyl radicals.
  • Aliphatic olefins are C 2 -Ci 2 - like C 2 -C 4 -olefins, such as ethylene, propene, but-1 -ene, but-2-ene, 2-methylprop-1 -ene,
  • Substituted aliphatic olefins are aliphatic olefins as defined herein, substituted by 1 , 2 or 3 substituents, preferably one substituent, which are independently selected from the group consisting of halogen, alkyl, substituted alkyl, cycloalkyl, aryl, and OH.
  • Cyclic olefins are C 3 -C 20 -, like C 3 -C 8 - or C 4 -Ci 2 - cyclic olefins, such as cyclopropene, cyclobutene, cyclobutadiene, cyclopentadiene, cyclohexene, cyclohexadiene, cyclooctene, cyclooctadiene; "Substituted cyclic olefins” are cyclic olefins as defined herein, substituted by 1 , 2 or 3 substituents, preferably one substituent, which are independently selected from the group consisting of halogen, alkyl, substituted alkyl, cycloalkyl, aryl, and OH.
  • Aryl represents a 6- to 12-membered, in particular 6- to 10-membered, aromatic cyclic radical. Examples thereof are: C 6 -Ci 2 -aryl such as phenyl
  • Substituted aryl is an aryl group as defined herein substituted with 1 , 2, 3, 4, or 5 substituents, in particular 1 , 2, 3 substituents, preferably one or two substituents, which are independently selected from the group consisting of halogen, alkyl, substituted alkyl, alkoxy and OH.
  • Arylene represents a 6- to 12-membered, in particular 6- to 10-membered aromatic cyclic diradical. Examples thereof are: C 6 -Ci 2 -arylene such as 1 ,2-phenylene and 2,3- naphthylene.
  • Substituted arylene is an arylene group as defined herein substituted with 1 , 2, 3 substituents, preferably one substituent, which are independently selected from the group consisting of halogen, alkyl, substituted alkyl, alkoxy and OH.
  • Alkoxy represents a radical of the formula R-0-, wherein R is a linear or branched alkyl group having from 1 to 6, in particular 1 to 4 carbon atoms.
  • R is a linear or branched alkyl group having from 1 to 6, in particular 1 to 4 carbon atoms.
  • CrC 6 -alkoxy radicals selected from methoxy, ethoxy, n-propoxy, isopropoxy, n- butoxy, 2-butoxy, iso-butoxy (2-methylpropoxy), tert-butoxy pentyloxy, 1 - methylbutoxy, 2 methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1 -ethyl propoxy, hexyloxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethylpropoxy, 1 -methylpentyloxy, 2- methylpentyloxy, 3-methylpentyloxy, 4 methylpentyloxy, 1 ,1 -dimethylbuty
  • 1 ,3-Dialkyldionate denotes the anion of 1 ,3-dialkylcarbonyl of general formula R- C(0)-CH 2 -C(0)-R, wherein R is an alkyl radical having from 1 to 6, preferably from 1 to 4, carbon atoms as defined herein. Examples thereof are 1 ,3-di-CrC 4 -alkyl-dionate such as acetylacetonate and 2,2,6,6-tetramethyl-3,5-heptanedionate.
  • Alkanoate represents a radical R-C(0)-0 " , wherein R is an alkyl radical having from 1 to 6, preferably from 1 to 4, carbon atoms as defined herein. Examples thereof are CrC 4 -alkanoate such as acetate
  • COD cyclooctadien
  • COT cyclooctatetraene
  • NBD bycyclo[2.2.1]hepta-2,5-dien (Norbornadiene)
  • acac acetylacetonate
  • dmfm dimethyl fumarate.
  • menthone refers to anyone of the possible stereoisomers such as:
  • isopulegol refers to anyone of the possible stereoisomers such as:
  • a ruthenium catalyst which is obtainable by contacting in situ in a liquid medium a ruthenium precursor which has labile ligands and a phenol derivative of formula (I)
  • R 1 , R 2 , R 3 independently are hydrogen, alkyl, like d-Ci 0 -alkyl (e.g. methyl, tertbutyl, nonyl) or hydroxy;
  • Y is a chemical bond, optionally substituted alkylene like Ci-C 8 - alkylene (e.g. -C(Me 2 )-), optionally substituted arylene like optionally substituted phenylene, (e.g. 1 ,2-phenylene), -0-, or S-;
  • R 4 is hydrogen, alkyl, like CrCi 0 -alkyl (e.g. methyl), hydroxy or optionally substituted aryl, like optionally substituted phenyl, (e.g. phenyl), or
  • R 3 , Y-R 4 together with the carbon atoms to which they are bound form an anellated aromatic ring
  • X is a chemical bond, optionally substituted alkylene, like Ci-C 8 - alkylene (e.g. -CH 2 -), optionally substituted arylene like optionally substituted phenylene, (e.g. 1 ,2-phenylene), -0-, or S-, and R 5 is hydrogen, alkyl, like CrCi 0 -alkyl (e.g. methyl, tertbutyl, nonyl), hydroxy, or an optionally substituted aryl, like optionally substituted C 6 -Ci2-aryl, (e.g. phenyl, 2-hydroxy-phenyl, 2-hydroxy-3,5- dimethyl-phenyl, 2-hydroxy-3,5-ditertbutyl-phenyl, 2-hydroxy- naphthyl), or
  • R 5 , R 4 together are optionally substituted arylene, like optionally substituted phenylene, (e.g. 4-methyl-6-hydroxy-1 ,2-phenylene).
  • alkyl like Ci-Cio-alkyl (e.g. methyl, tertbutyl, nonyl), or hydroxy, or
  • an anellated aromatic ring e.g. phenyl
  • Ci-Cio-alkyl e.g. methyl, tertbutyl, nonyl
  • hydroxy e.g. methyl, tertbutyl, nonyl
  • alkylene like Ci-C 8 - alkylene (e.g. -CMe 2 -), optionally substituted arylene, like optionally substituted phenylene (e.g. 1 ,2-phenylene), -0-, or - S-;
  • Ci-Ci 0 -alkyl e.g. methyl, tertbutyl, nonyl
  • an anellated aromatic ring e.g. phenyl
  • alkylene like Ci-C 8 - alkylene (e.g. -CMe 2 -), optionally substituted arylene like optionally substituted phenylene (e.g. 1 ,2-phenylene), -0-, or - S-.
  • arylene like optionally substituted phenylene (e.g. 1 ,2-phenylene), -0-, or - S-.
  • R 1 , R 2 , R 3 , R 4 independently are hydrogen, branched or linear alkyl, like C
  • Cio-alkyl e.g. tBu, Me, nonyl
  • hydroxy e.g.
  • R 3 , R 4 together with the carbon atoms to which they are bound form an anellated aromatic ring (e.g. phenyl);
  • R 5a is hydrogen, branched or linear alkyl, like Ci-Ci 0 -alkyl (e.g. tBu,
  • Y is a chemical bond or optionally substituted alkylene, like Ci-C 8 - alkylene (e.g. -CMe 2 -), preferably optionally substituted alkylene (e.g. -CMe 2 -);
  • R 6 , R 7 , R 8 , R 9 independently are hydrogen or branched or linear alkyl , like C
  • Cio-alkyl e.g. tBu, Me
  • Cio-alkyl e.g. tBu, Me
  • R 6 , R 7 together with the carbon atoms to which they are bound form an anellated aromatic ring (e.g. phenyl);
  • R 10 is hydrogen or hydroxy
  • X is a chemical bond, optionally substituted alkylene, like optionally substituted phenylene (e.g. -CH 2 -), or -0-.
  • R 1 , R 3 independently are hydrogen, linear or branched alkyl, like CrCi 0 -alkyl (e.g. methyl, tertbutyl, nonyl), or hydroxy.
  • R 2 is hydrogen or linear or branched alkyl, like CrCi 0 -alkyl (e.g. methyl, tertbutyl, nonyl), in particular hydrogen or methyl.
  • R 4 is hydrogen or linear or branched alkyl, like CrCi 0 -alkyl (e.g. methyl, tertbutyl, nonyl), in particular hydrogen, or R 3 , R 4 together with the carbon atoms to which they are bound form an anellated aromatic ring, in particular a phenyl ring.
  • CrCi 0 -alkyl e.g. methyl, tertbutyl, nonyl
  • R 6 is hydrogen or linear or branched alkyl, like CrCi 0 -alkyl (e.g. methyl, tertbutyl, nonyl), in particular hydrogen.
  • R 7 , R 9 independently are hydrogen, linear or branched alkyl, like CrCi 0 -alkyl
  • R 8 is hydrogen or linear or branched alkyl, like CrCi 0 -alkyl (e.g. methyl, tertbutyl, nonyl), in particular hydrogen or methyl.
  • R 1 , R 2 , R 3 , R 4 and R 5a independently are hydrogen, alkyl, like C-i-C-io- alkyl, or hydroxy.
  • R 1 , R 3 independently are hydrogen, linear Ci-Ci 0 -alkyl (e.g. methyl, nonyl), branched C 3 -Ci 0 -alkyl (e.g. tertbutyl), or hydroxy.
  • R is hydrogen, linear Ci-Cio-alkyl (e.g. methyl, nonyl), or branched C 3 -Ci 0 -alkyl (e.g. tertbutyl), in particular hydrogen.
  • R 4 is hydrogen, linear Ci-Cio-alkyl (e.g. methyl, nonyl), or branched C 3 -Ci 0 -alkyl (e.g. tertbutyl), in particular hydrogen.
  • R is hydrogen, linear Ci-Cio-alkyl (e.g. methyl, nonyl), branched C 3 -Ci 0 -alkyl (e.g. tertbutyl), or hydroxy.
  • RR 1 , R 2 , R 3 independently are hydrogen or alkyl.
  • Y is a chemical bond, optionally substituted alkylene, like Ci-C 8 - alkylene (e.g. -CMe 2 -), optionally substituted arylene, like optionally substituted phenylene, -0-, or -S-;
  • R 7 , R 8 , R 9 independently are hydrogen or alkyl, like Ci-Ci 0 -alkyl
  • X is a chemical bond, optionally substituted alkylene, like Ci-C 8 - alkylene (e.g. -CMe 2 -), optionally substituted arylene, like optionally substituted phenylene, -0-, or -S-.
  • R 1 , R 2 , R 3 independently are hydrogen, linear Ci-Ci 0 -alkyl, or branched
  • Y is optionally substituted alkylene, preferably alkylene like Ci-C 8 - alkylene, (e.g. -CMe 2 -);
  • R 7 , R 8 , R 9 independently are hydrogen, linear Ci-Ci 0 -alkyl, or branched
  • R 10 is hydrogen or hydroxy
  • X is -0-.
  • R 1 , R 3 are hydrogen.
  • R 2 is hydrogen, linear Ci-Cio-alkyl (e.g. methyl, nonyl), or branched C 3 -Ci 0 -alkyl (e.g. tertbutyl), in particular methyl.
  • R 7 , R 9 are hydrogen.
  • R 8 is hydrogen, linear Ci-Cio-alkyl (e.g. methyl, nonyl), or branched C 3 -Ci 0 -alkyl (e.g. tertbutyl), in particular methyl.
  • R 1 , R 2 , R 3 , R 4 independently are hydrogen or alkyl, like Ci-Ci 0 -alkyl, or
  • R 3 , R 4 together with the carbon atoms to which they are bound form an anellated aromatic ring, preferably a phenyl ring;
  • R 6 , R 7 , R 8 , R 9 independently are hydrogen or alkyl, like Ci-Ci 0 -alkyl, or R 6 , R 7 together with the carbon atoms to which they are bound form an anellated aromatic ring, preferably a phenyl ring;
  • R 10 is hydrogen or hydroxy
  • X is a chemical bond, optionally substituted alkylene, like Ci-C 8 - alkylene (e.g. -CH 2 -), optionally substituted arylene, like optionally substituted phenylene, -0-, or -S-.
  • R 1 , R 2 , R 3 , R 4 independently are hydrogen, linear Ci-Ci 0 -alkyl, or branched
  • R 3 , R 4 together with the carbon atoms to which they are bound form an anellated aromatic ring, preferably a phenyl ring;
  • R 6 , R 7 , R 8 , R 9 independently are hydrogen, linear Ci-Ci 0 -alkyl, or branched
  • R 6 , R 7 together with the carbon atoms to which they are bound form an anellated aromatic ring, preferably a phenyl ring;
  • R 10 is hydrogen or hydroxy
  • X is a chemical bond or alkylene, like CrC 8 -alkylene (e.g. -CH 2 -).
  • R 2 is hydrogen
  • R 4 is hydrogen, or R 4 , R 3 together with the carbon atoms to which they are bound form an anellated aromatic ring, preferably a phenyl ring.
  • R 6 is hydrogen, or R 6 , R 7 together with the carbon atoms to which they are bound form an anellated aromatic ring, preferably a phenyl ring.
  • R is hydrogen.
  • the phenol derivative of formula (I) is nonyl phenol, 2,2'-biphenol, or
  • Ru is in the oxidation state (+II), (+III) or (+IV);
  • each ligand L independently is hydride, halide (e.g. CI, Br, I), alkyl, like C 1 -C 10 - alkyl, optionally substituted aliphatic olefins like C 2 -Ci 2 -olefins, (e.g. methyl allyl, 2,4-dimethylpentadienyl, 2,7-dimethyl-2,6-octadiene, dodecatriene), optionally substituted cyclic olefins, like C 4 -Ci 0 -cyclic olefins, (e.g. cyclooctadiene, cyclopentadienyl, pentamethylcyclopentadienyl), -CO, 1 ,3-dialkyldionate (e.g.
  • acetylacetonate 2,2,6,6-tetramethyl-3,5-heptanedionate
  • alkanoate like CrC 6 -alkanoate, (e.g. acetate), or optionally substituted aryl (e.g. benzene, p-cymene);
  • n is an integer in a range from 2 to 6;
  • n is at least 1 ,
  • optionally substituted alkylene represents alkylene optionally substituted by 1 , 2 or 3 substituents which are independently selected from the group consisting of halogen, alkyl, substituted alkyl, cycloalkyl, aryl, and OH
  • optionally substituted arylene represents arylene optionally substituted by 1 , 2, 3 substituents which are independently selected from the group consisting of halogen, alkyl, substituted alkyl, alkoxy and OH
  • optionally substituted aryl represents aryl optionally substituted by 1 , 2, 3, 4 or 5 substituents, in particular 1 , 2, 3 substituents which are independently selected from the group consisting of halogen, alkyl, substituted alkyl, alkoxy and OH
  • optionally substituted aliphatic olefins represents aliphatic olefins optionally substituted by 1 , 2 or 3 substituents which are independently selected from the group consisting of
  • cyclooctadiene cyclopentadienyl, pentamethylcyclopentadienyl
  • -CO 1 ,3-dialkyldionate (e.g. acetylacetonate, 2,2,6,6-tetramethyl-3,5-heptanedionate), alkanoate like Ci-C 6 - alkanoate, (e.g. acetate), or optionally substituted aryl (e.g. benzene, p- cymene).
  • 1 ,3-dialkyldionate e.g. acetylacetonate, 2,2,6,6-tetramethyl-3,5-heptanedionate
  • alkanoate like Ci-C 6 - alkanoate, (e.g. acetate), or optionally substituted aryl (e.g. benzene, p- cymene).
  • the transfer hydrogenation reaction is the isomerization of unsaturated alcohols, the isomerization of unsaturated carbonyl, the hydrogenation of alkenes, the hydrogenation of ketones, the dehydrogenation of alcohols, a dehydrogenating esterification, the dehydrogenating coupling of alcohols with amines to amides, the alkylation of amines with alcohols, or the oxidation of alcohols to aldehydes.
  • the transfer hydrogenation reaction is the isomerization of unsaturated alcohols, the isomerization of unsaturated aldehydes, the hydrogenation of alkenes, the hydrogenation of ketones, or the dehydrogenation of alcohols.
  • a method for preparing menthone wherein a dehydrogenation/hydrogenation reaction is carried out in the liquid phase using isopulegol, a ruthenium precursor according to any one of embodiments 10 to 16 and a phenol derivative of formula (I) according to any one of embodiments 1 to 9.
  • the amount of ruthenium in the ruthenium catalyst of any one of claims 1 to 16 is in the range from 50 to 3000, preferably 100 to 1000, more preferably is 200 to 600 ppm by weight based on the total liquid reaction mixture in the reaction space.
  • the weight ratio between the phenol derivative and isopulegol is 1 :10.
  • reaction is carried out at a temperature in the range from 100 to 220°C, preferably 150 to 200°C. More preferably, the reaction is carried out at a temperature in the range from 170 to 190°C.
  • the ruthenium precursors are commercially available or can be easily prepared following standard chemistry. See for example J. Powell, B. L. Shaw, J. Chem. Soc. A: Inorganic, Physical, Theoretical 1968, 7, 159 - 161 ; M. O. Albers, E. Singleton, J. E. Yates, Inorg. Synthesis 1989, 26, 249 - 258; R. Grobelny, B. Jezowska-Trzebiatowska, W. Wojchiechowski J. Inorg. Nucl. Chem. 1966, 28, 2715 - 2718; A. Endo, K. Shimizu, G. P. Sato, M. Mukaida Chem. Lett. 1984, 437 - 440.
  • the ruthenium catalyst according to the invention is used in transfer hydrogenation reactions such as the isomerization of unsaturated alcohols, the isomerization of unsaturated carbonyl, the hydrogenation of alkenes, the hydrogenation of ketones, the dehydrogenation of alcohols, a dehydrogenating esterification, the dehydrogenating coupling of alcohols with amines to amides, the alkylation of amines with alcohols, or the oxidation of alcohols to aldehydes.
  • transfer hydrogenation reactions such as the isomerization of unsaturated alcohols, the isomerization of unsaturated carbonyl, the hydrogenation of alkenes, the hydrogenation of ketones, the dehydrogenation of alcohols, a dehydrogenating esterification, the dehydrogenating coupling of alcohols with amines to amides, the alkylation of amines with alcohols, or the oxidation of alcohols to aldehydes.
  • unsaturated alcohols compounds comprising at least a double
  • R 1 3 ⁇ 4 H alkyl, substituted alkyl, aryl, substitutecl aryl
  • R M H alkyl, substituted alkyl, aryl, substitutecl aryl
  • R alkyl
  • R 2 K Alkyl, Aryl
  • R 3 H alkyl, siisstituted alkyl, aryl, substitutecl aryl
  • R 1 2 H alkyl, substituted alkyl, aryl, substituted aryl
  • dehydrogenating esterification compounds comprising at least one primary alcohol are reacted with a further primary or secondary alcohol in presence of the catalyst according to the invention.
  • Representative non limiting examples of dehydrogenating esterifications are reported in the scheme below.
  • R H alkyl, substituted alkyl, aryl, substituted aryl
  • R 1 ⁇ H alkyl, substituted alkyl, aryl, substituted aryl
  • the invention is illustrated by the following non-limiting examples: Experimental section General information:
  • A Bis(2-methylallyl)(1 ,5-cylcooctadiene)ruthenium(ll).
  • B Ruthenium(lll) acetyl acetonate (Ruacac).
  • Example 1 Isomerization of unsaturated Exampless - Isopulegol to Menthone/lsomenthone
  • GC analyses were performed using an Agilent 6890 equipped with a VF-23ms column (60m, 0.25 mm, 0.25 ⁇ ).
  • Total selectivity selectivity of menthone + selectivity of isomenthone + selectivity of pulegone + selectivity of menthol).
  • the ruthenium-phosphanyl-complexes were synthesized according to the literature (S. P. Nolan, T. R. Belderrain and R. H. Grubbs Organometallics 1997, 16, 5569 - 5571 ).
  • Example 1.8 Ruthenium precursor A and phenol derivative 1 as catalyst
  • Isopulegol, A or rather B and the phenol derivative 1 , 2 or 3 were placed in a 100ml Schlenk-flask equipped with a magnetic stirring bar. At ambient pressure the mixture was heated at 180°C and stirred for the reaction time t-i .
  • Comparative example 1.36 Ruthenium precursor A and phenol derivative 1 (pre- synthesized and isolated catalyst) Under semi-inert conditions 0,5 g A and 1 ,93 g of the phenol derivative 1 were placed in a 30ml Schlenk-flask equipped with a magnetic stirring bar. At ambient pressure the mixture was heated at 160°C and stirred for 30 minutes. After cooling down to room temperature an orange-brown solid was obtained and purified by silica gel column chromatography using heptane as eluent. 38,2 mg ( 300 ppm [Ru]) of the obtained greyish solid together with 9 g isopulegol were then placed in a 30 ml Schlenk-flask.
  • Example 2 Hydrogenation of unsaturated bonds / Dehvdrogenation of Examples:
  • Example 2.1 1-Octene to Octane
  • Carrier gas Helium
  • L-Pulegone L-Menthone D-lsomenthone Analytical Method (see example 1 ) Under semi-inert conditions 1 g L-pulegone, 8 g 2-propanol, 1 g 1 and 9,5 mg A were placed in a 50ml glass autoclave equipped with a paddle stirrer. At inherent pressure the mixture was heated at 180°C and stirred for 5 hours. A L-pulegone conversion of 88% and a menthone selectivity of 93,6% were determined via calibrated GC analysis.
  • GC analyses were performed using an Agilent6890 equipped with an Optima-1 column (30m, 0.32 mm, 0.5 ⁇ ).
  • Carrier gas Helium
  • GC analyses were performed using an Agilent6890 equipped with an Optima-1 column (30m, 0.32 mm, 0.5 ⁇ ).
  • Carrier gas Helium

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Abstract

La présente invention concerne un catalyseur qui peut être obtenu par mise en contact in situ d'un précurseur de ruthénium et d'un dérivé de phénol. En outre, la présente invention concerne l'utilisation dudit catalyseur dans des réactions d'hydrogénation. In particulier, la présente invention concerne un procédé de préparation de menthone à partir d'isopulégol.
EP15707938.5A 2014-03-05 2015-03-04 Catalyseurs ruthénium-phénol pour des réactions d'hydrogénation par transfert Active EP3113879B1 (fr)

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CN107721833B (zh) * 2017-10-18 2020-11-20 万华化学集团股份有限公司 一种制备薄荷酮的方法
CN109593029B (zh) * 2018-11-26 2022-01-07 万华化学集团股份有限公司 一种制备高纯度l-薄荷酮的方法及用于该方法的催化剂体系
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